Site icon Adaptive Digital Framework

An accurate and efficient framework for modelling the surface chemistry of ionic materials

An accurate and efficient framework for modelling the surface chemistry of ionic materials
  • Nørskov, J. K., Bligaard, T., Rossmeisl, J. & Christensen, C. H. Towards the computational design of solid catalysts. Nat. Chem. 1, 37–46 (2009).

    PubMed 

    Google Scholar 

  • Patel, H. A., Byun, J. & Yavuz, C. T. Carbon dioxide capture adsorbents: chemistry and methods. ChemSusChem 10, 1303–1317 (2017).

    CAS 
    PubMed 

    Google Scholar 

  • Rosen, A. S. et al. Tuning the redox activity of metal–organic frameworks for enhanced, selective O2 binding: design rules and ambient temperature O2 chemisorption in a cobalt–triazolate framework. J. Am. Chem. Soc. 142, 4317–4328 (2020).

    CAS 
    PubMed 

    Google Scholar 

  • Bligaard, T. et al. The Brønsted–Evans–Polanyi relation and the volcano curve in heterogeneous catalysis. J. Catal. 224, 206–217 (2004).

    CAS 

    Google Scholar 

  • Michaelides, A. et al. Identification of general linear relationships between activation energies and enthalpy changes for dissociation reactions at surfaces. J. Am. Chem. Soc. 125, 3704–3705 (2003).

    CAS 
    PubMed 

    Google Scholar 

  • Sauer, J. Ab initio calculations for molecule–surface interactions with chemical accuracy. Acc. Chem. Res. 52, 3502–3510 (2019).

    CAS 
    PubMed 

    Google Scholar 

  • Kubas, A. et al. Surface adsorption energetics studied with “gold standard” wave-function-based ab initio methods: small-molecule binding to TiO2(110). J. Phys. Chem. Lett. 7, 4207–4212 (2016).

    CAS 
    PubMed 

    Google Scholar 

  • Araujo, R. B., Rodrigues, G. L. S., dos Santos, E. C. & Pettersson, L. G. M. Adsorption energies on transition metal surfaces: towards an accurate and balanced description. Nat. Commun. 13, 6853 (2022).

    CAS 
    PubMed 
    PubMed Central 

    Google Scholar 

  • Hamada, I. Van der Waals density functional made accurate. Phys. Rev. B 89, 121103 (2014).

    Google Scholar 

  • Platero, E. E., Scarano, D., Spoto, G. & Zecchina, A. Dipole coupling and chemical shifts of CO and NO adsorbed on oxides and halides with rock-salt structure. Faraday Discuss. Chem. Soc. 80, 183–193 (1985).

    Google Scholar 

  • Di Valentin, C. et al. NO monomers on MgO powders and thin films. J. Phys. Chem. B 106, 1637–1645 (2002).

    Google Scholar 

  • Hamlyn, R. C. E. et al. Imaging the ordering of a weakly adsorbed two-dimensional condensate: ambient-pressure microscopy and spectroscopy of CO2 molecules on rutile TiO2(110). Phys. Chem. Chem. Phys. 20, 13122–13126 (2018).

    CAS 
    PubMed 

    Google Scholar 

  • Meixner, D. L., Arthur, D. A. & George, S. M. Kinetics of desorption, adsorption, and surface diffusion of CO2 on MgO(100). Surf. Sci. 261, 141–154 (1992).

    CAS 

    Google Scholar 

  • Chakradhar, A. & Burghaus, U. Carbon dioxide adsorption on MgO(001)–CO2 kinetics and dynamics. Surf. Sci. 616, 171–177 (2013).

    CAS 

    Google Scholar 

  • Pacchioni, G., Ricart, J. M. & Illas, F. Ab initio cluster model calculations on the chemisorption of CO2 and SO2 probe molecules on MgO and CaO (100) surfaces. A theoretical measure of oxide basicity. J. Am. Chem. Soc. 116, 10152–10158 (1994).

    CAS 

    Google Scholar 

  • Jensen, M. B., Pettersson, L. G. M., Swang, O. & Olsbye, U. CO2 sorption on MgO and CaO surfaces: a comparative quantum chemical cluster study. J. Phys. Chem. B 109, 16774–16781 (2005).

    CAS 
    PubMed 

    Google Scholar 

  • Downing, C. A., Sokol, A. A. & Catlow, C. R. A. The reactivity of CO2 on the MgO(100) surface. Phys. Chem. Chem. Phys. 16, 184–195 (2013).

    Google Scholar 

  • Mazheika, A. & Levchenko, S. V. Ni substitutional defects in bulk and at the (001) surface of MgO from first-principles calculations. J. Phys. Chem. C 120, 26934–26944 (2016).

    CAS 

    Google Scholar 

  • Yanagisawa, Y., Takaoka, K., Yamabe, S. & Ito, T. Interaction of CO2 with magnesium oxide surfaces: a TPD, FTIR, and cluster-model calculation study. J. Phys. Chem. 99, 3704–3710 (1995).

    CAS 

    Google Scholar 

  • Sorescu, D. C., Lee, J., Al-Saidi, W. A. & Jordan, K. D. CO2 adsorption on TiO2(110) rutile: insight from dispersion-corrected density functional theory calculations and scanning tunneling microscopy experiments. J. Chem. Phys. 134, 104707 (2011).

    PubMed 

    Google Scholar 

  • Huesges, Z., Müller, C., Paulus, B. & Maschio, L. Dispersion corrected DFT calculations for the adsorption of N2O on MgO. Surf. Sci. 627, 11–15 (2014).

    CAS 

    Google Scholar 

  • Shi, B. X., Wales, D. J., Michaelides, A. & Myung, C. W. Going for gold(-standard): attaining coupled cluster accuracy in oxide-supported nanoclusters. J. Chem. Theory Comput. 20, 5306–5316 (2024).

    CAS 
    PubMed 

    Google Scholar 

  • Campbell, C. T. & Sellers, J. R. V. Enthalpies and entropies of adsorption on well-defined oxide surfaces: experiment measurements. Chem. Rev. 113, 4106–4135 (2013).

    CAS 
    PubMed 

    Google Scholar 

  • Grimme, S., Antony, J., Ehrlich, S. & Krieg, H. A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu. J. Chem. Phys. 132, 154104 (2010).

    PubMed 

    Google Scholar 

  • Ehlert, S. et al. r2SCAN-D4: dispersion corrected meta-generalized gradient approximation for general chemical applications. J. Chem. Phys. 154, 061101 (2021).

    CAS 
    PubMed 

    Google Scholar 

  • Ning, J. et al. Workhorse minimally empirical dispersion-corrected density functional with tests for weakly bound systems: r2SCAN + rVV10. Phys. Rev. B 106, 075422 (2022).

    CAS 

    Google Scholar 

  • Bučko, T., Lebègue, S., Ángyán, J. G. & Hafner, J. Extending the applicability of the Tkatchenko-Scheffler dispersion correction via iterative Hirshfeld partitioning. J. Chem. Phys. 141, 034114 (2014).

    PubMed 

    Google Scholar 

  • Klimeš, J., Kaltak, M., Maggio, E. & Kresse, G. Singles correlation energy contributions in solids. J. Chem. Phys. 143, 102816 (2015).

    PubMed 

    Google Scholar 

  • Ehrlich, S., Moellmann, J., Reckien, W., Bredow, T. & Grimme, S. System-dependent dispersion coefficients for the DFT-D3 treatment of adsorption processes on ionic surfaces. ChemPhysChem 12, 3414–3420 (2011).

    CAS 
    PubMed 

    Google Scholar 

  • Kothakonda, M. et al. Testing the r2SCAN density functional for the thermodynamic stability of solids with and without a van der Waals correction. ACS Mater. Au 3, 102–111 (2023).

    CAS 
    PubMed 

    Google Scholar 

  • Shi, B. X. et al. Many-body methods for surface chemistry come of age: achieving consensus with experiments. J. Am. Chem. Soc. 145, 25372–25381 (2023).

    CAS 
    PubMed 
    PubMed Central 

    Google Scholar 

  • Ye, H.-Z. & Berkelbach, T. C. Ab initio surface chemistry with chemical accuracy. Preprint at (2024).

  • Karalti, O., Alfè, D., Gillan, M. J. & Jordan, K. D. Adsorption of a water molecule on the MgO(100) surface as described by cluster and slab models. Phys. Chem. Chem. Phys. 14, 7846–7853 (2012).

    CAS 
    PubMed 

    Google Scholar 

  • Alessio, M., Usvyat, D. & Sauer, J. Chemically accurate adsorption energies: CO and H2O on the MgO(001) surface. J. Chem. Theory Comput. 15, 1329–1344 (2019).

    CAS 
    PubMed 

    Google Scholar 

  • Lu, Y. et al. Multiscale QM/MM modelling of catalytic systems with ChemShell. Phys. Chem. Chem. Phys. 25, 21816–21835 (2023).

    CAS 
    PubMed 

    Google Scholar 

  • Jain, A. et al. Commentary: the Materials Project: a materials genome approach to accelerating materials innovation. APL Mater 1, 011002 (2013).

    Google Scholar 

  • Ye, H.-Z. & Berkelbach, T. C. Adsorption and vibrational spectroscopy of CO on the surface of MgO from periodic local coupled-cluster theory. Faraday Discuss 254, 628–640 (2024).

    CAS 
    PubMed 
    PubMed Central 

    Google Scholar 

  • Campbell, C. T. & Sellers, J. R. V. The entropies of adsorbed molecules. J. Am. Chem. Soc. 134, 18109–18115 (2012).

    CAS 
    PubMed 

    Google Scholar 

  • Kirkpatrick, J. et al. Pushing the frontiers of density functionals by solving the fractional electron problem. Science 374, 1385–1389 (2021).

    CAS 
    PubMed 

    Google Scholar 

  • Sheldon, C., Paier, J., Usvyat, D. & Sauer, J. Hybrid RPA:DFT approach for adsorption on transition metal surfaces: methane and ethane on platinum (111). J. Chem. Theory Comput. 20, 2219–2227 (2024).

    PubMed 
    PubMed Central 

    Google Scholar 

  • Sillar, K., Hofmann, A. & Sauer, J. Ab initio study of hydrogen adsorption in MOF-5. J. Am. Chem. Soc. 131, 4143–4150 (2009).

    CAS 
    PubMed 

    Google Scholar 

  • Berger, F., Rybicki, M. & Sauer, J. Adsorption and cracking of propane by zeolites of different pore size. J. Catal. 395, 117–128 (2021).

    CAS 

    Google Scholar 

  • Wichtendahl, R., Rodriguez-Rodrigo, M., Härtel, U., Kuhlenbeck, H. & Freund, H.-J. Thermodesorption of CO and NO from vacuum-cleaved NiO(100) and MgO(100). Phys. Status Solidi A 173, 93–100 (1999).

    CAS 

    Google Scholar 

  • Dohnálek, Z., Kim, J., Bondarchuk, O., White, J. M. & Kay, B. D. Physisorption of N2, O2, and CO on fully oxidized TiO2(110). J. Phys. Chem. B 110, 6229–6235 (2006).

    PubMed 

    Google Scholar 

  • Shi, B. X. et al. General embedded cluster protocol for accurate modeling of oxygen vacancies in metal-oxides. J. Chem. Phys. 156, 124704 (2022).

    CAS 
    PubMed 

    Google Scholar 

  • Nagy, P. R. & Kállay, M. Approaching the basis set limit of CCSD(T) energies for large molecules with local natural orbital coupled-cluster methods. J. Chem. Theory Comput. 15, 5275–5298 (2019).

    CAS 
    PubMed 

    Google Scholar 

  • Riplinger, C. & Neese, F. An efficient and near linear scaling pair natural orbital based local coupled cluster method. J. Chem. Phys. 138, 034106 (2013).

    PubMed 

    Google Scholar 

  • Rosen, A. Quacc – the quantum accelerator. Zenodo (2024).

  • Sauer, J. Molecular models in ab initio studies of solids and surfaces: from ionic crystals and semiconductors to catalysts. Chem. Rev. 89, 199–255 (1989).

    CAS 

    Google Scholar 

  • Bogdanov, N. A., Li Manni, G., Sharma, S., Gunnarsson, O. & Alavi, A. Enhancement of superexchange due to synergetic breathing and hopping in corner-sharing cuprates. Nat. Phys. 18, 190–195 (2022).

    CAS 

    Google Scholar 

  • Dittmer, A., Izsák, R., Neese, F. & Maganas, D. Accurate band gap predictions of semiconductors in the framework of the similarity transformed equation of motion coupled cluster theory. Inorg. Chem. 58, 9303–9315 (2019).

    CAS 
    PubMed 
    PubMed Central 

    Google Scholar 

  • Chizallet, C. et al. Assignment of photoluminescence spectra of MgO powders: TD-DFT cluster calculations combined to experiments. Part I: structure effects on dehydroxylated surfaces. J. Phys. Chem. C 112, 16629–16637 (2008).

    CAS 

    Google Scholar 

  • Chung, L. W. et al. The ONIOM method and its applications. Chem. Rev. 115, 5678–5796 (2015).

    CAS 
    PubMed 

    Google Scholar 

  • Neese, F., Wennmohs, F., Becker, U. & Riplinger, C. The ORCA quantum chemistry program package. J. Chem. Phys. 152, 224108 (2020).

    CAS 
    PubMed 

    Google Scholar 

  • Kállay, M. et al. The MRCC program system: accurate quantum chemistry from water to proteins. J. Chem. Phys. 152, 074107 (2020).

    PubMed 

    Google Scholar 

  • Neese, F. & Valeev, E. F. Revisiting the atomic natural orbital approach for basis sets: robust systematic basis sets for explicitly correlated and conventional correlated ab initio methods. J. Chem. Theory Comput. 7, 33–43 (2011).

    CAS 
    PubMed 

    Google Scholar 

  • Kresse, G. & Furthmüller, J. Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set. Comput. Mater. Sci. 6, 15–50 (1996).

    CAS 

    Google Scholar 

  • Kresse, G. & Furthmüller, J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys. Rev. B 54, 11169–11186 (1996).

    CAS 

    Google Scholar 

  • Li, Y.-P., Gomes, J., Mallikarjun Sharada, S., Bell, A. T. & Head-Gordon, M. Improved force-field parameters for QM/MM simulations of the energies of adsorption for molecules in zeolites and a free rotor correction to the rigid rotor harmonic oscillator model for adsorption enthalpies. J. Phys. Chem. C 119, 1840–1850 (2015).

    CAS 

    Google Scholar 

  • Sun, Q. & Chan, G. K.-L. Quantum embedding theories. Acc. Chem. Res. 49, 2705–2712 (2016).

    CAS 
    PubMed 

    Google Scholar 

  • Lau, B. T. G., Knizia, G. & Berkelbach, T. C. Regional embedding enables high-level quantum chemistry for surface science. J. Phys. Chem. Lett. 12, 1104–1109 (2021).

    CAS 
    PubMed 

    Google Scholar 

  • Schäfer, T., Libisch, F., Kresse, G. & Grüneis, A. Local embedding of coupled cluster theory into the random phase approximation using plane waves. J. Chem. Phys. 154, 011101 (2021).

    PubMed 

    Google Scholar 

  • Huang, Z. et al. Advancing surface chemistry with large-scale ab-initio quantum many-body simulations. Preprint at (2025).

  • Al-Hamdani, Y. S. et al. Interactions between large molecules pose a puzzle for reference quantum mechanical methods. Nat. Commun. 12, 3927 (2021).

    CAS 
    PubMed 
    PubMed Central 

    Google Scholar 

  • Schäfer, T., Irmler, A., Gallo, A. & Grüneis, A. Understanding discrepancies of wavefunction theories for large molecules. Preprint at (2024).

  • Shi, B. X. et al. Systematic discrepancies between reference methods for noncovalent interactions within the S66 dataset. J. Chem. Phys. 162, 144107 (2025).

    CAS 
    PubMed 

    Google Scholar 

  • Cui, Z.-H., Zhai, H., Zhang, X. & Chan, G. K.-L. Systematic electronic structure in the cuprate parent state from quantum many-body simulations. Science 377, 1192–1198 (2022).

    CAS 
    PubMed 

    Google Scholar 

  • Shi, B. X. et al. Supporting data for ‘An accurate and efficient framework for modelling the surface chemistry of ionic materials’. Zenodo (2025).

  • Günster, J., Liu, G., Stultz, J. & Goodman, D. W. Interaction of methanol and water on MgO(100) studied by ultraviolet photoelectron and metastable impact electron spectroscopies. J. Chem. Phys. 110, 2558–2565 (1999).

    Google Scholar 

  • Stirniman, M. J., Huang, C., Scott Smith, R., Joyce, S. A. & Kay, B. D. The adsorption and desorption of water on single crystal MgO(100): the role of surface defects. J. Chem. Phys. 105, 1295–1298 (1996).

    CAS 

    Google Scholar 

  • Thompson, T. L., Diwald, O. & Yates, J. T. CO2 as a probe for monitoring the surface defects on TiO2(110) temperature-programmed desorption. J. Phys. Chem. B 107, 11700–11704 (2003).

    CAS 

    Google Scholar 

  • Lian, J. C. et al. N2O adsorption on the surface of MgO(001) thin films: an infrared and TPD study. J. Phys. Chem. C 114, 3148–3151 (2010).

    CAS 

    Google Scholar 

  • link

    Exit mobile version